Adhesive formulations that are free of asphalt or substantially free of asphalt, methods of making the same, and roofing systems utilizing the same

ABSTRACT

Some embodiments of the present disclosure relate to roofing systems including a substrate and adhesive formulations that are free of asphalt or substantially free of asphalt. Some embodiments of the present disclosure relate to methods of making one or more adhesive formulations that are free of asphalt or substantially free of asphalt. Some embodiments of the present disclosure relate to systems utilizing one or more adhesive formulations that are free of asphalt or substantially free of asphalt.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to: U.S. Provisional Patent ApplicationNo. 63/074,358, filed Sep. 3, 2020, and titled “ADHESIVE FORMULATIONSTHAT ARE FREE OF ASPHALT OR SUBSTANTIALLY FREE OF ASPHALT, METHODS OFMAKING THE SAME, AND ROOFING SYSTEMS UTILIZING THE SAME;” U.S.Provisional Patent Application No. 63/104,150, filed Oct. 22, 2020, andtitled “ADHESIVE FORMULATIONS THAT ARE FREE OF ASPHALT OR SUBSTANTIALLYFREE OF ASPHALT, METHODS OF MAKING THE SAME, AND ROOFING SYSTEMSUTILIZING THE SAME;” and priority to U.S. Provisional Patent ApplicationNo. 63/168,879, filed Mar. 31, 2021, and titled “ADHESIVE FORMULATIONSTHAT ARE FREE OF ASPHALT OR SUBSTANTIALLY FREE OF ASPHALT, METHODS OFMAKING THE SAME, AND ROOFING SYSTEMS UTILIZING THE SAME;” thedisclosures of which applications are hereby incorporated herein byreference in their entireties.

FIELD

The field of the present disclosure relates to adhesive formulationsthat are free of asphalt or substantially free of asphalt. In onenon-limiting example, the adhesive formulations described herein may beutilized in the roofing arts.

BACKGROUND

Asphaltic adhesives are used in various areas, such as but not limitedto, as sealants for roofing shingles. However, asphaltic adhesives mayrequire elevated temperatures for activation, making their useimpractical in certain circumstances.

SUMMARY

Some embodiments of the present disclosure relate to an adhesiveformulation that is free or substantially free of asphalt. In someembodiments, the adhesive formulation comprises at least one process oiland at least one polymer. In some embodiments, the adhesive formulationcomprises limestone powder, at least one process oil, and at least onepolymer. In some embodiments, the adhesive formulation comprises atleast one tackifier, at least one process oil, and at least one polymer.

Some embodiments of the present disclosure relate to a method of makingan adhesive formulation that is free or substantially free of asphalt.In some embodiments, the method comprises combining at least one processoil and at least one polymer. In some embodiments, the method comprisescombining limestone powder with at least one process oil and at leastone polymer. In some embodiments, the method comprises combining atleast one tackifier with at least one process oil and at least onepolymer.

Some embodiments of the present disclosure relate to a method of usingan adhesive formulation that is free or substantially free of asphalt.

Some embodiments of the present disclosure relate to a system comprisinga substrate and an adhesive formulation, where the adhesive formulationis free or substantially free of asphalt, and where the adhesiveformulation is present on at least one surface of the substrate.

In some embodiments, a method includes combining limestone powder withat least one process oil and at least one polymer, so as to form anadhesive formulation. In some embodiments, the adhesive formulationincludes 10 wt % to 60 wt % of the limestone powder based on a totalweight of the adhesive formulation; 20 wt % to 70 wt % of the at leastone process oil based on the total weight of the adhesive formulation;and 0.5 wt % to 30 wt % of the at least one polymer based on a totalweight of the adhesive formulation. In some embodiments, the adhesiveformulation is free of asphalt or substantially free of asphalt.

In some embodiments, the at least one process oil is chosen from atleast one paraffinic oil, at least one petroleum extract, at least onevegetable oil, at least one naphthenic oil, at least one aromatic oil,at least one re-refined engine oil bottom (REOB), at least one engineoil residue (EOR), at least one re-refined heavy vacuum distillationbottom (RHVDB), at least one re-refined heavy vacuum distillation oil(RHVDO), at least one re-refined vacuum tower bottom (RVTB), at leastone vacuum tower bottom (VTB), at least one tall oil, or any combinationthereof.

In some embodiments, the at least one polymer is astyrene-butadiene-styrene (SBS) copolymer.

In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 30 wt % based on the total weight of the adhesiveformulation.

In some embodiments, the adhesive formulation includes at least onesecond polymer chosen from: at least one polyolefin, oxidizedpolyethylene (OPE), polyethylene-polypropylene elastomer, ground tirerubber (GTR), isotactic polypropylene (IPP), atactic polypropylene(APP), or any combination thereof.

In some embodiments, the at least one second polymer is present in anamount of 0.1 wt % to 20 wt % based on the total weight of the adhesiveformulation.

In some embodiments, the adhesive formulation includes at least onefiller in an amount ranging from 0.00001% to 70% by weight of theadhesive formulation.

In some embodiments, the at least one filler is calcium carbonate,barium sulfate, calcium sulfate, talc, perlite, silica, fumed silica,precipitated silica, quartz, aluminum trihydrate, magnesium hydroxide,colemanite, titanium dioxide, snow white, fly ash, graphenenanoparticles, carbon black, recycled rubber tires, recycled shingles,recycled thermoplastic resins, basalt, roofing granules, clay, ammoniumpolyphosphate, graphite, or any combination thereof.

In some embodiments, the adhesive formulation includes at least oneadditive in an amount ranging from 0.00001% to 70% by weight of theadhesive formulation.

In some embodiments, the at least one additive is at least one wax, atleast one antioxidant, ethylene-bis-stearamide (EBS), or any combinationthereof.

In some embodiments, the adhesive formulation achieves at least apassing grade when tested according to ASTM D1970 at a specific testtemperature.

In some embodiments, the passing grade is 2 lb/ft at the specific testtemperature of 40° F.

In some embodiments, the passing grade is 12 lb/ft at the specific testtemperature of 75 ° F.

In some embodiments, the method includes applying the adhesiveformulation to at least one surface of a substrate.

In some embodiments, the substrate is a plywood substrate, a glasssubstrate, a cellulosic substrate, a roofing shingle, an underlayment, aroofing membrane, a roof deck, a photovoltaic (PV) panel, a modifiedbitumen (MODBIT) substrate, a roll good, a polyisocyanurate (ISO) foamboard, a chimney or any combination thereof.

In some embodiments, the method includes forming the adhesiveformulation into at least one adhesive sheet, forming the adhesiveformulation into at least one adhesive strip, or any combinationthereof.

In some embodiments, the forming of the adhesive formulation into atleast one adhesive sheet, the forming the adhesive formulation into atleast one adhesive strip, or any combination thereof includes castingthe adhesive formulation into the at least one adhesive sheet, castingthe adhesive formulation into the at least one adhesive strip, or anycombination thereof.

In some embodiments, the method includes forming the adhesiveformulation into a flowable adhesive formulation, wherein the flowableadhesive formulation has a viscosity of 1,000 cP to 10,000 cP measuredat 374° F., using a Brookfield viscometer with spindle number LV-4, anda viscometer speed of 60 RPM.

In some embodiments, the method includes forming the adhesiveformulation into a flowable adhesive formulation, wherein the flowableadhesive formulation has a viscosity of 10,000 cP to 30,000 cP measuredat 374° F., using a Brookfield viscometer with spindle number LV-4, anda viscometer speed of 30 RPM.

In some embodiments, the method includes forming the adhesiveformulation into a flowable adhesive formulation, wherein the forming ofthe flowable adhesive formulation includes heating the adhesiveformulation to a temperature of 300° F. to 400° F.

In some embodiments, the method includes using the adhesive formulationto seal a leak.

In some embodiments, the leak is present on a surface of a substrate,between multiple surfaces of a substrate, between multiple substrates,or any combination thereof.

In some embodiments, the substrate, the multiple substrates, or anycombination thereof is a roofing substrate.

In some embodiments, the roofing substrate is a roofing shingle.

In some embodiments, an adhesive formulation includes 10 wt % to 60 wt %of limestone powder based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation includes 20 wt % to 70 wt% of at least one process oil based on the total weight of the adhesiveformulation. In some embodiments, the adhesive formulation includes 0.5wt % to 30 wt % of at least one polymer based on the total weight of theadhesive formulation. In some embodiments, the adhesive formulation isfree of asphalt or substantially free of asphalt.

In some embodiments, an adhesive formulation consists essentially of 10wt % to 60 wt % of limestone powder based on a total weight of theadhesive formulation; 20 wt % to 70 wt % of at least one process oilbased on the total weight of the adhesive formulation; and 0.5 wt % to30 wt % of at least one polymer based on the total weight of theadhesive formulation. In some embodiments, the adhesive formulationachieves at least a passing grade of 2 lb/ft when tested according toASTM D1970 at a specific test temperature of 40° F.

In some embodiments, an adhesive formulation consists essentially of 10wt % to 60 wt % of limestone powder based on a total weight of theadhesive formulation; 20 wt % to 70 wt % of at least one process oilbased on a total weight of the adhesive formulation; and 0.5 wt % to 30wt % of at least one polymer based on a total weight of the adhesiveformulation. In some embodiments, the adhesive formulation achieves atleast a passing grade of 12 lb/ft when tested according to ASTM D1970 ata specific test temperature of 75° F.

In some embodiments, a system includes a substrate; and an adhesiveformulation. In some embodiments, the adhesive formulation is present onat least one surface of the substrate. In some embodiments, the adhesiveformulation includes 10 wt % to 60 wt % of limestone powder based on atotal weight of the adhesive formulation; 20 wt % to 70 wt % of at leastone process oil based on the total weight of the adhesive formulation;and 0.5 wt % to 30 wt % of at least one polymer based on the totalweight of the adhesive formulation. In some embodiments, the adhesiveformulation is free of asphalt or substantially free of asphalt.

In some embodiments, the substrate is a first substrate, the systemincludes a second substrate, and the adhesive formulation is presentbetween the first substrate and the second substrate.

In some embodiments, the first substrate and the second substrate arethe same.

In some embodiments, the first substrate and the second substrate aredifferent.

In some embodiments, the first substrate, the second substrate, or anycombination thereof is a roofing shingle.

In some embodiments, a method includes combining at least one tackifierwith at least one process oil and at least one polymer, so as to form anadhesive formulation. In some embodiments, the adhesive formulationincludes 10 wt % to 60 wt % of the at least one tackifier based on atotal weight of the adhesive formulation; 20 wt % to 70 wt % of the atleast one process oil based on the total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of the at least one polymer basedon the total weight of the adhesive formulation. In some embodiments,the adhesive formulation is free of asphalt or substantially free ofasphalt.

In some embodiments, the at least one process oil is chosen from atleast one paraffinic oil, at least one petroleum extract, at least onevegetable oil, at least one naphthenic oil, at least one aromatic oil,at least one re-refined engine oil bottom (REOB), at least one engineoil residue (EOR), at least one re-refined heavy vacuum distillationbottom (RHVDB), at least one re-refined heavy vacuum distillation oil(RHVDO), at least one re-refined vacuum tower bottom (RVTB), at leastone vacuum tower bottom (VTB), or any combination thereof.

In some embodiments, the at least one process oil is at least one talloil.

In some embodiments, the at least one tall oil takes the form of talloil pitch.

In some embodiments, the at least one tackifier is at least one rosinester.

In some embodiments, the at least one rosin ester is at least onepentaerythritol rosin ester.

In some embodiments, the at least one rosin ester is at least oneglycerol rosin ester.

In some embodiments, the at least one tackifier is chosen from: at leastone terpene resin, at least one petroleum resin, at least onehydrogenated rosin, at least one rosin milk, at least one petroleumresin emulsion, at least one terpene-phenolic resin, at least onehydrogenated petroleum resin, at least one liphatic hydrocarbon resin,at least one hydrogenated aliphatic hydrocarbon resin, at least onearomatic modified aliphatic hydrocarbon resin, at least one hydrogenatedaromatic modified aliphatic hydrocarbon resin, at least onepolycyclopentadiene resin, at least one hydrogenated polycyclopentadieneresin, at least one cycloaliphatic hydrocarbon resin, at least onehydrogenated cycloaliphatic resin, cycloaliphatic/aromatic hydrocarbonresin, at least one hydrogenated cycloaliphatic/aromatic hydrocarbonresin, hydrogenated aromatic hydrocarbon resin, at least one maleicacid/anhydride modified tackifier, terpene modified aromatic and/oraliphatic hydrocarbon resin, at least one hydrogenated terpene modifiedaromatic and/or aliphatic hydrocarbon resin, at least one polyterpeneresin, at least one hydrogenated polyterpene resin, at least onearomatic modified polyterpene resin, at least one hydrogenated aromaticmodified polyterpene resin, at least one terpene-phenol resin, at leastone hydrogenated terpene-phenol resin, at least one gum rosin resin, atleast one hydrogenated gum rosin resin, at least one gum rosin esterresin, at least one wood rosin resin, at least one hydrogenated woodrosin resin, at least one rosin acid resin, at least one hydrogenatedrosin acid resin, or any combination thereof.

In some embodiments, the at least one polymer is astyrene-butadiene-styrene (SBS) copolymer.

In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 30 wt % based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation includes at least onesecond polymer, wherein the second polymer is astyrene-ethylene-butylene-styrene (SEBS) copolymer.

In some embodiments, the at least one second polymer is present in anamount of 0.1 wt % to 20 wt % based on a total weight of the adhesiveformulation.

In some embodiments, an adhesive formulation includes 10 wt % to 60 wt %of at least one tackifier based on a total weight of the adhesiveformulation; 20 wt % to 70 wt % of at least one process oil based on thetotal weight of the adhesive formulation; and 0.5 wt % to 30 wt % of atleast one polymer based on the total weight of the adhesive formulation.In some embodiments, the adhesive formulation is free of asphalt orsubstantially free of asphalt.

In some embodiments, an adhesive formulation consists essentially of 10wt % to 60 wt % of at least one tackifier based on a total weight of theadhesive formulation; 20 wt % to 70 wt % of at least one process oilbased on the total weight of the adhesive formulation; and 0.5 wt % to30 wt % of at least one polymer based on the total weight of theadhesive formulation. In some embodiments, the adhesive formulationachieves a mechanical uplift of at least 20 lb/ft when tested accordingto ASTM D6381 after being conditioned at 140° F. for 16 hours.

In some embodiments, the adhesive formulation achieves a mechanicaluplift of 20 lb/ft to 100 lb/ft when tested according to ASTM D6381after being conditioned at 140° F. for 16 hours.

In some embodiments, the adhesive formulation has an activationtemperature of 15° F. to 60° F.

In some embodiments, the adhesive formulation has a Dahlquist CriterionTemperature of 35° F. to 65° F.

In some embodiments, the adhesive formulation has a peel strength of 7.5MPa to 50 MPa measured at 25° C.

In some embodiments, a system includes a substrate; and an adhesiveformulation. In some embodiments, the adhesive formulation is present onat least one surface of the substrate. In some embodiments, the adhesiveformulation includes 10 wt % to 60 wt % of at least one tackifier basedon a total weight of the adhesive formulation; 20 wt % to 70 wt % of atleast one process oil based on the total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of at least one polymer based onthe total weight of the adhesive formulation. In some embodiments, theadhesive formulation is free of asphalt or substantially free ofasphalt.

In some embodiments, the substrate is a first substrate, wherein thesystem includes a second substrate, and wherein the adhesive formulationis present between the first substrate and the second substrate.

In some embodiments, the first substrate and the second substrate arethe same.

In some embodiments, the first substrate and the second substrate aredifferent.

In some embodiments, the first substrate is a TPO substrate.

In some embodiments, the second substrate is an ETFE substrate.

In some embodiments, an adhesive formulation includes 10 wt % to 60 wt %of limestone powder, at least one tackifier, or any combination thereofbased on a total weight of the adhesive formulation; 20 wt % to 70 wt %of at least one process oil based on a total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of at least one polymer based on atotal weight of the adhesive formulation. In some embodiments, theadhesive formulation is free of asphalt or substantially free ofasphalt.

In some embodiments, an adhesive formulation includes 10 wt % to 60 wt %of limestone powder, at least one tackifier, or any combination thereofbased on a total weight of the adhesive formulation; 20 wt % to 70 wt %of at least one process oil based on the total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of at least one first polymer basedon the total weight of the adhesive formulation; and 0.1 wt % to 20 wt %of at least one second polymer based on the total weight of the adhesiveformulation. In some embodiments, the adhesive formulation is free ofasphalt or substantially free of asphalt.

In some embodiments, an adhesive formulation includes 20 wt % to 70 wt %of at least one process oil based on a total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of at least one polymer based onthe total weight of the adhesive formulation. In some embodiments, theadhesive formulation is free of asphalt or substantially free ofasphalt.

In some embodiments, an adhesive formulation includes 20 wt % to 70 wt %of at least one process oil based on a total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of at least onestyrene-butadiene-styrene (SBS) copolymer based on the total weight ofthe adhesive formulation. In some embodiments, the adhesive formulationis free of asphalt or substantially free of asphalt.

In some embodiments, an adhesive formulation includes 20 wt % to 70 wt %of tall oil based on a total weight of the adhesive formulation; 0.5 wt% to 30 wt % of at least one styrene-butadiene-styrene (SBS) copolymerbased on the total weight of the adhesive formulation; and 0.1 wt % to20 wt % of at least one styrene-ethylene-butylene-styrene (SEBS)copolymer based on the total weight of the adhesive formulation. In someembodiments, the adhesive formulation is free of asphalt orsubstantially free of asphalt.

In some embodiments, an adhesive formulation consists essentially of 10wt % to 60 wt % of limestone powder, at least one tackifier, or anycombination thereof based on a total weight of the adhesive formulation;20 wt % to 70 wt % of at least one process oil based on the total weightof the adhesive formulation; 0.5 wt % to 30 wt % of at least one polymerbased on the total weight of the adhesive formulation; and optionally,0.1 wt % to 30 wt % of at least one second polymer based on the totalweight of the adhesive formulation.

In some embodiments, an adhesive formulation consists essentially of 20wt % to 70 wt % of at least one process oil based on a total weight ofthe adhesive formulation; 0.5 wt % to 30 wt % of at least onestyrene-butadiene-styrene (SBS) copolymer based on the total weight ofthe adhesive formulation; 10 wt % to 60 wt % of: limestone powder, atleast one tackifier, or optionally, any combination thereof, based onthe total weight of the adhesive formulation; and optionally, 0.1 wt %to 20 wt % of at least one styrene-ethylene-butylene-styrene (SEBS)copolymer based on the total weight of the adhesive formulation.

In some embodiments, an adhesive formulation consists essentially of 20wt % to 70 wt % of at least one first process oil based on a totalweight of the adhesive formulation, wherein the at least one firstprocess oil is tall oil; 0.5 wt % to 30 wt % of at least onestyrene-butadiene-styrene (SBS) copolymer based on the total weight ofthe adhesive formulation; 10 wt % to 60 wt % of at least one tackifierbased on the total weight of the adhesive formulation; optionally, 10 wt% to 60 wt % of limestone powder based on the total weight of theadhesive formulation; optionally, 0.1 wt % to 20 wt % of at least onestyrene-ethylene-butylene-styrene (SEBS) copolymer based on the totalweight of the adhesive formulation; and optionally, 20 wt % to 70 wt %of at least one second process oil based on the total weight of theadhesive formulation.

In some embodiments, an adhesive formulation consists essentially of 20wt % to 70 wt % of at least one first process oil based on a totalweight of the adhesive formulation; 0.5 wt % to 30 wt % of at least onefirst polymer based on the total weight of the adhesive formulation; 10wt % to 60 wt % of at least one tackifier based on the total weight ofthe adhesive formulation; optionally, 10 wt % to 60 wt % of limestonepowder based on the total weight of the adhesive formulation;optionally, 0.1 wt % to 20 wt % of at least one second polymer based onthe total weight of the adhesive formulation; and optionally, 20 wt % to70 wt % of at least one second process oil based on the total weight ofthe adhesive formulation.

In some embodiments, a method includes combining limestone powder withat least one process oil and at least one polymer, so as to form anadhesive formulation. In some embodiments, the adhesive formulationincludes 10 wt % to 60 wt % of the limestone powder, at least onetackifier or any combination thereof, based on a total weight of theadhesive formulation; 0.1 wt % to 50 wt % of at least one fire retardantbased on the total weight of the adhesive formulation; 20 wt % to 70 wt% of the at least one process oil based on the total weight of theadhesive formulation; and 0.5 wt % to 30 wt % of the at least onepolymer based on the total weight of the adhesive formulation. In someembodiments, the adhesive formulation is free of asphalt orsubstantially free of asphalt.

In some embodiments, an adhesive formulation includes 10 wt % to 60 wt %of limestone powder, at least one tackifier, or any combination thereofbased on a total weight of the adhesive formulation; 20 wt % to 70 wt %of at least one process oil based on the total weight of the adhesiveformulation; 0.1 wt % to 50 wt % of at least one fire retardant based onthe total weight of the adhesive formulation; and 0.5 wt % to 30 wt % ofat least one polymer based on the total weight of the adhesiveformulation. In some embodiments, the adhesive formulation is free ofasphalt or substantially free of asphalt.

In some embodiments, a system includes a substrate; and an adhesiveformulation, wherein the adhesive formulation is present on at least onesurface of the substrate. In some embodiments, the adhesive formulationincludes 10 wt % to 60 wt % of limestone powder, at least one tackifier,or any combination thereof based on a total weight of the adhesiveformulation; 20 wt % to 70 wt % of at least one process oil based on thetotal weight of the adhesive formulation; 0.1 wt % to 50 wt % of atleast one fire retardant based on the total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of at least one polymer based onthe total weight of the adhesive formulation. In some embodiments, theadhesive formulation is free of asphalt or substantially free ofasphalt.

In some embodiments, a method, includes combining a filler with at leastone process oil and at least one polymer, so as to form an adhesiveformulation. In some embodiments, the adhesive formulation includes 10wt % to 70 wt % of the filler based on a total weight of the adhesiveformulation. In some embodiments, the adhesive formulation includes 20wt % to 70 wt % of the at least one process oil based on a total weightof the adhesive formulation. In some embodiments, the adhesiveformulation includes 0.5 wt % to 30 wt % of the at least one polymerbased on a total weight of the adhesive formulation. In someembodiments, the adhesive formulation is free of asphalt orsubstantially free of asphalt.

In some embodiments, the at least one process oil is chosen from atleast one paraffinic oil, at least one petroleum extract, at least onevegetable oil, at least one naphthenic oil, at least one aromatic oil,at least one re-refined engine oil bottom (REOB), at least one engineoil residue (EOR), at least one re-refined heavy vacuum distillationbottom (RHVDB), at least one re-refined heavy vacuum distillation oil(RHVDO), at least one re-refined vacuum tower bottom (RVTB), at leastone vacuum tower bottom (VTB), at least one tall oil, or any combinationthereof.

In some embodiments, the at least one polymer is astyrene-butadiene-styrene (SBS) copolymer.

In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 30 wt % based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation includes at least onesecond polymer chosen from: at least one polyolefin, oxidizedpolyethylene (OPE), polyethylene-polypropylene elastomer, ground tirerubber (GTR), isotactic polypropylene (IPP), atactic polypropylene(APP), or any combination thereof.

In some embodiments, the at least one second polymer is present in anamount of 0.1 wt % to 20 wt % based on a total weight of the adhesiveformulation.

In some embodiments, the at least one filler is limestone powder,calcium carbonate, barium sulfate, calcium sulfate, talc, perlite,silica, fumed silica, precipitated silica, quartz, aluminum trihydrate,magnesium hydroxide, colemanite, titanium dioxide, snow white, fly ash,graphene nanoparticles, carbon black, recycled rubber tires, recycledshingles, recycled thermoplastic resins, basalt, roofing granules, clay,ammonium polyphosphate, graphite, or any combination thereof.

In some embodiments, the at least one filler is limestone powder.

In some embodiments, the adhesive formulation includes at least oneadditive in an amount ranging from 0.00001% to 70% by weight of theadhesive formulation.

In some embodiments, the at least one additive is at least one wax, atleast one antioxidant, ethylene-bis-stearamide (EBS), or any combinationthereof.

In some embodiments, the adhesive formulation includes 0.1 wt % to 50wt.% of at least one fire retardant based on a total weight of theadhesive formulation.

In some embodiments, a method includes combining a filler with at leastone process oil and at least one polymer, so as to form an adhesiveformulation. In some embodiments, the adhesive formulation includes 10wt % to 70 wt % of the filler, at least one tackifier or any combinationthereof, based on a total weight of the adhesive formulation. In someembodiments, the adhesive formulation includes 0.1 wt % to 50 wt % of atleast one fire retardant based on a total weight of the adhesiveformulation. In some embodiments, the adhesive formulation includes 20wt % to 70 wt % of the at least one process oil based on a total weightof the adhesive formulation. In some embodiments, the adhesiveformulation includes 0.5 wt % to 30 wt % of the at least one polymerbased on a total weight of the adhesive formulation. In someembodiments, the adhesive formulation is free of asphalt orsubstantially free of asphalt.

In some embodiments, the at least one process oil is chosen from atleast one paraffinic oil, at least one petroleum extract, at least onevegetable oil, at least one naphthenic oil, at least one aromatic oil,at least one re-refined engine oil bottom (REOB), at least one engineoil residue (EOR), at least one re-refined heavy vacuum distillationbottom (RHVDB), at least one re-refined heavy vacuum distillation oil(RHVDO), at least one re-refined vacuum tower bottom (RVTB), at leastone vacuum tower bottom (VTB), at least one tall oil, or any combinationthereof.

In some embodiments, the at least one polymer is astyrene-butadiene-styrene (SBS) copolymer.

In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 30 wt % based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation includes at least onesecond polymer chosen from: at least one polyolefin, oxidizedpolyethylene (OPE), polyethylene-polypropylene elastomer, ground tirerubber (GTR), isotactic polypropylene (IPP), atactic polypropylene(APP), or any combination thereof.

In some embodiments, the at least one second polymer is present in anamount of 0.1 wt % to 20 wt % based on a total weight of the adhesiveformulation.

In some embodiments, the at least one filler is limestone powder.

In some embodiments, a system includes a substrate and an adhesiveformulation. In some embodiments, the adhesive formulation is present onat least one surface of the substrate. In some embodiments, the adhesiveformulation includes 10 wt % to 70 wt % of a filler, at least onetackifier, or any combination thereof based on a total weight of theadhesive formulation. In some embodiments, the adhesive formulationincludes 20 wt % to 70 wt % of at least one process oil based on a totalweight of the adhesive formulation. In some embodiments, the adhesiveformulation includes 0.1 wt % to 50 wt % of at least one fire retardantbased on a total weight of the adhesive formulation. In someembodiments, the adhesive formulation includes 0.5 wt % to 30 wt % of atleast one polymer based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation is free of asphalt orsubstantially free of asphalt.

In some embodiments, the substrate is a plywood substrate, a glasssubstrate, a fiberglass substrate, a cellulosic substrate, a shingle, anunderlayment, a roofing membrane, a roof deck, a photovoltaic (PV)panel, a modified bitumen (MODBIT) substrate, a rolled good, or anycombination thereof.

Covered embodiments are defined by the claims, not the above summary.The above summary is a high-level overview of various aspects andintroduces some of the concepts that are further described in theDetailed Description section below. This summary is not intended toidentify key or essential features of the claimed subject matter, nor isit intended to be used in isolation to determine the scope of theclaimed subject matter. The subject matter should be understood byreference to appropriate portions of the entire specification, any orall drawings, and each claim.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an exemplary adhesive formulation according to someembodiments of the present disclosure.

FIG. 2 depicts an exemplary system using an exemplary adhesiveformulation according to some embodiments of the present disclosure.

Some embodiments of the disclosure are herein described, by way ofexample only, with reference to the accompanying drawings. With specificreference now to the drawings in detail, it is stressed that theembodiments shown are by way of example and for purposes of illustrativediscussion of embodiments of the disclosure. In this regard, thedescription taken with the drawings makes apparent to those skilled inthe art how embodiments of the disclosure may be practiced.

DETAILED DESCRIPTION

Some embodiments of the present disclosure relate to an adhesiveformulation that is free of asphalt or substantially free of asphalt.

As used herein, an adhesive formulation is “free of asphalt” when nodetectable asphalt is present in the formulation.

As used herein, an adhesive formulation is “substantially free ofasphalt” when no more than a specific amount of asphalt is present inthe formulation. In some embodiments, the specific amount of asphalt isat most 5% of asphalt by weight based on a total weight of theformulation. In some embodiments, the specific amount of asphalt is atmost 1% of asphalt by weight based on a total weight of the formulation.In some embodiments, the specific amount of asphalt is at most 0.5% ofasphalt by weight based on a total weight of the formulation. In someembodiments, the specific amount of asphalt is at most 0.05% of asphaltby weight based on a total weight of the formulation. In someembodiments, the specific amount of asphalt is at most 0.005% of asphaltby weight based on a total weight of the formulation. In someembodiments, “substantially free of asphalt” means the amount of asphaltadded would not materially change the characteristics of at least oneproperty of the adhesive formulation. In some embodiments,“substantially free of asphalt” means the amount of asphalt added wouldnot materially change the characteristics of at least two properties ofthe adhesive formulation.

In some embodiments, the adhesive formulation comprises at least oneprocess oil.

In some embodiments, the at least one process oil is chosen from or isselected from the group consisting of: at least one paraffinic oil, atleast one petroleum extract, at least one vegetable oil, at least onenaphthenic oil, at least one aromatic oil, at least one re-refinedengine oil bottom (REOB), at least one engine oil residue (EOR), atleast one re-refined heavy vacuum distillation bottom (RHVDB), at leastone re-refined heavy vacuum distillation oil (RHVDO), at least onere-refined vacuum tower bottom (RVTB), at least one vacuum tower bottom(VTB), at least one tall oil, or any combination thereof.

In some embodiments, the at least one process oil is chosen from or isselected from the group consisting of at least one paraffinic oil, atleast one petroleum extract, at least one vegetable oil, at least onenaphthenic oil, at least one aromatic oil, at least one re-refinedengine oil bottom (REOB), at least one engine oil residue (EOR), atleast one re-refined heavy vacuum distillation bottom (RHVDB), at leastone re-refined heavy vacuum distillation oil (RHVDO), at least onere-refined vacuum tower bottom (RVTB), at least one vacuum tower bottom(VTB), or any combination thereof.

In some embodiments, the at least one process oil, comprises, consistsessentially of, or consists of at least one tall oil. In someembodiments, the at least one tall oil comprises consists essentiallyof, or consists of tall oil pitch.

In some embodiments, the adhesive formulation comprises 20 wt % to 70 wt% of the at least one process oil based on a total weight of theadhesive formulation. In some embodiments, the adhesive formulationcomprises 30 wt % to 70 wt % of the at least one process oil based on atotal weight of the adhesive formulation. In some embodiments, theadhesive formulation comprises 40 wt % to 70 wt % of the at least oneprocess oil based on a total weight of the adhesive formulation. In someembodiments, the adhesive formulation comprises 50 wt % to 70 wt % ofthe at least one process oil based on a total weight of the adhesiveformulation. In some embodiments, the adhesive formulation comprises 60wt % to 70 wt % of the at least one process oil based on a total weightof the adhesive formulation.

In some embodiments, the adhesive formulation comprises 20 wt % to 60 wt% of the at least one process oil based on a total weight of theadhesive formulation. In some embodiments, the adhesive formulationcomprises 20 wt % to 50 wt % of the at least one process oil based on atotal weight of the adhesive formulation. In some embodiments, theadhesive formulation comprises 20 wt % to 40 wt % of the at least oneprocess oil based on a total weight of the adhesive formulation. In someembodiments, the adhesive formulation comprises 20 wt % to 30 wt % ofthe at least one process oil based on a total weight of the adhesiveformulation.

In some embodiments, the adhesive formulation comprises 30 wt % to 60 wt% of the at least one process oil based on a total weight of theadhesive formulation. In some embodiments, the adhesive formulationcomprises 40 wt % to 50 wt % of the at least one process oil based on atotal weight of the adhesive formulation.

In some embodiments, the at least one process oil comprises saturates,aromatics, resins, asphaltenes, or any combination thereof.

In some embodiments, the at least one process oil comprises saturates inan amount ranging from 5 wt % to 99 wt % based on a total weight of theat least one process oil. In some embodiments, the at least one processoil comprises saturates in an amount ranging from 25 wt % to 99 wt %based on a total weight of the at least one process oil. In someembodiments, the at least one process oil comprises saturates in anamount ranging from 50 wt % to 99 wt % based on a total weight of the atleast one process oil. In some embodiments, the at least one process oilcomprises saturates in an amount ranging from 75 wt % to 99 wt % basedon a total weight of the at least one process oil.

In some embodiments, the at least one process oil comprises saturates inan amount ranging from 5 wt % to 75 wt % based on a total weight of theat least one process oil. In some embodiments, the at least one processoil comprises saturates in an amount ranging from 5 wt % to 50 wt %based on a total weight of the at least one process oil. In someembodiments, the at least one process oil comprises saturates in anamount ranging from 5 wt % to 25 wt % based on a total weight of the atleast one process oil.

In some embodiments, the at least one process oil comprises saturates inan amount ranging from 25 wt % to 50 wt % based on a total weight of theat least one process oil.

In some embodiments, the at least one process oil comprises aromatics inan amount ranging from 0 wt % to 99 wt % based on a total weight of theat least one process oil. In some embodiments, the at least one processoil comprises aromatics in an amount ranging from 25 wt % to 99 wt %based on a total weight of the at least one process oil. In someembodiments, the at least one process oil comprises aromatics in anamount ranging from 50 wt % to 99 wt % based on a total weight of the atleast one process oil. In some embodiments, the at least one process oilcomprises aromatics in an amount ranging from 75 wt % to 99 wt % basedon a total weight of the at least one process oil.

In some embodiments, the at least one process oil comprises aromatics inan amount ranging from 0 wt % to 75 wt % based on a total weight of theat least one process oil. In some embodiments, the at least one processoil comprises aromatics in an amount ranging from 0 wt % to 50 wt %based on a total weight of the at least one process oil. In someembodiments, the at least one process oil comprises aromatics in anamount ranging from 0 wt % to 25 wt % based on a total weight of the atleast one process oil.

In some embodiments, the at least one process oil comprises aromatics inan amount ranging from 25 wt % to 50 wt % based on a total weight of theat least one process oil.

In some embodiments, the at least one process oil comprises resins in anamount ranging from 0 wt % to 25 wt % based on a total weight of the atleast one process oil. In some embodiments, the at least one process oilcomprises resins in an amount ranging from 10 wt % to 25 wt % based on atotal weight of the at least one process oil. In some embodiments, theat least one process oil comprises resins in an amount ranging from 20wt % to 25 wt % based on a total weight of the at least one process oil.

In some embodiments, the at least one process oil comprises resins in anamount ranging from 0 wt % to 20 wt % based on a total weight of the atleast one process oil. In some embodiments, the at least one process oilcomprises resins in an amount ranging from 0 wt % to 10 wt % based on atotal weight of the at least one process oil.

In some embodiments, the at least one process oil comprises resins in anamount ranging from 10 wt % to 20 wt % based on a total weight of the atleast one process oil.

In some embodiments, the at least one process oil comprises asphaltenesin an amount ranging from 0 wt % to 30 wt % based on a total weight ofthe at least one process oil. In some embodiments, the at least oneprocess oil comprises asphaltenes in an amount ranging from 10 wt % to30 wt % based on a total weight of the at least one process oil. In someembodiments, the at least one process oil comprises asphaltenes in anamount ranging from 20 wt % to 30 wt % based on a total weight of the atleast one process oil.

In some embodiments, the at least one process oil comprises asphaltenesin an amount ranging from 0 wt % to 20 wt % based on a total weight ofthe at least one process oil. In some embodiments, the at least oneprocess oil comprises asphaltenes in an amount ranging from 0 wt % to 10wt % based on a total weight of the at least one process oil.

In some embodiments, the at least one process oil comprises asphaltenesin an amount ranging from 10 wt % to 20 wt % based on a total weight ofthe at least one process oil.

Non-limiting examples of commercially available process oils andexemplary constituents of the commercially available process oils arereproduced below in Table 1.

TABLE 1 Non-limiting Examples of Commercial Process Oils andConstituents thereof: Saturates Aromatics Resins Asphaltenes CommercialProcess Oil (wt %) (wt %) (wt %) (wt %) Kendex ® 0866 2010 6.7 85.7 7.50 Hydrolene ™ H600T 13.1 80.1 5.9 0.9 Kendex ® 0834 10.2 69.8 13.5 6.4Kendex ® MNE 41.9 56.4 1.7 0 Kendex ® 0842 24.1 50.1 21.4 4.4 Cross ™Oil L-3500 33.9 44.8 0.7 0 Raffene ® 2000 53 42.6 4.4 0 Kendex ® 0898 4241.5 12.7 3.8 Kendex ® 0897 57.4 35.2 5.9 1.5 Uninap ® 818 74.8 25.2 0 0Hydrolene ™ 75.9 23.3 0.8 0 Kendex ® 0847 73.7 22.2 2.9 0 Safety Kleen ®RHT 240 93.3 2 2.3 2.4 Safety Kleen ® (Normal) 61.1 0 12.4 26.5Therminol Heating Oil 97.8 0 0 0

In some embodiments, the adhesive formulation comprises at least onepolymer.

In some embodiments, the at least one polymer is chosen from or selectedfrom the group consisting of: at least one polyolefin, oxidizedpolyethylene (OPE), polyethylene-polypropylene elastomer, ground tirerubber (GTR), isotactic polypropylene (IPP), atactic polypropylene(APP), or any combination thereof.

In some embodiments the at least one polymer comprises, consists, orconsists essentially of a styrene-butadiene-styrene (SBS) copolymer.

In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 30 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of1 wt % to 30 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of10 wt % to 30 wt % based on a total weight of the adhesive formulation.In some embodiments, the At least one polymer is present in an amount of15 wt % to 30 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of20 wt % to 30 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of25 wt % to 30 wt % based on a total weight of the adhesive formulation.

In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 25 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 20 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 15 wt % based on a total weight of the adhesive formulation.In some embodiments, the At least one polymer is present in an amount of0.5 wt % to 10 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 5 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of0.5 wt % to 1 wt % based on a total weight of the adhesive formulation.

In some embodiments, the at least one polymer is present in an amount of1 wt % to 25 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of5 wt % to 20 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one polymer is present in an amount of10 wt % to 15 wt % based on a total weight of the adhesive formulation.

In some embodiments, the at least one polymer is at least one firstpolymer and the adhesive formulation further comprises at least onesecond polymer.

In some embodiments, the at least one second polymer is chosen from orselected from the group consisting of at least one polyolefin, oxidizedpolyethylene (OPE), polyethylene-polypropylene elastomer, ground tirerubber (GTR), isotactic polypropylene (IPP), atactic polypropylene(APP), or any combination thereof.

In some embodiments, the at least one second polymer comprises,consists, or consists essentially of a styrene-ethylene-butylene-styrene(SEBS) copolymer.

In some embodiments, the at least one second polymer is present in anamount of 0.1 wt % to 20 wt % based on a total weight of the adhesiveformulation. In some embodiments, the at least one second polymer ispresent in an amount of 1 wt % to 20 wt % based on a total weight of theadhesive formulation. In some embodiments, the at least one secondpolymer is present in an amount of 5 wt % to 20 wt % based on a totalweight of the adhesive formulation. In some embodiments, the at leastone second polymer is present in an amount of 10 wt % to 20 wt % basedon a total weight of the adhesive formulation. In some embodiments, theat least one second polymer is present in an amount of 15 wt % to 20 wt% based on a total weight of the adhesive formulation.

In some embodiments, the at least one second polymer is present in anamount of 0.1 wt % to 15 wt % based on a total weight of the adhesiveformulation. In some embodiments, the at least one second polymer ispresent in an amount of 0.1 wt % to 10 wt % based on a total weight ofthe adhesive formulation. In some embodiments, the at least one secondpolymer is present in an amount of 0.1 wt % to 5 wt % based on a totalweight of the adhesive formulation. In some embodiments, the at leastone second polymer is present in an amount of 0.1 wt % to 1 wt % basedon a total weight of the adhesive formulation.

In some embodiments, the at least one second polymer is present in anamount of 1 wt % to 15 wt % based on a total weight of the adhesiveformulation. In some embodiments, the at least one second polymer ispresent in an amount of 5 wt % to 10 wt % based on a total weight of theadhesive formulation.

In some embodiments, the adhesive formulation further compriseslimestone powder.

In some embodiments, the adhesive formulation comprises 10 wt % to 60 wt% of the limestone powder based on a total weight of the adhesiveformulation. In some embodiments, the adhesive formulation comprises 20wt % to 60 wt % of the limestone powder based on a total weight of theadhesive formulation. In some embodiments, the adhesive formulationcomprises 30 wt % to 60 wt % of the limestone powder based on a totalweight of the adhesive formulation. In some embodiments, the adhesiveformulation comprises 40 wt % to 60 wt % of the limestone powder basedon a total weight of the adhesive formulation. In some embodiments, theadhesive formulation comprises 50 wt % to 60 wt % of the limestonepowder based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation comprises 10 wt % to 50 wt% of the limestone powder based on a total weight of the adhesiveformulation. In some embodiments, the adhesive formulation comprises 10wt % to 40 wt % of the limestone powder based on a total weight of theadhesive formulation. In some embodiments, the adhesive formulationcomprises 10 wt % to 30 wt % of the limestone powder based on a totalweight of the adhesive formulation. In some embodiments, the adhesiveformulation comprises 10 wt % to 20 wt % of the limestone powder basedon a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation comprises 20 wt % to 50 wt% of the limestone powder based on a total weight of the adhesiveformulation. In some embodiments, the adhesive formulation comprises 30wt % to 40 wt % of the limestone powder based on a total weight of theadhesive formulation.

In some embodiments, the adhesive formulation further comprises at leastone tackifier.

In some embodiments, the at least one tackifier is at least one rosinester. In some embodiments, the at least one rosin ester is at least onepentaerythritol rosin ester. In some embodiments, the at least one rosinester is at least one glycerol rosin ester.

In some embodiments, the at least one tackifier is chosen from orselected from the group consisting of at least one terpene resin, atleast one petroleum resin, at least one hydrogenated rosin, at least onerosin milk, at least one petroleum resin emulsion, at least oneterpene-phenolic resin, at least one hydrogenated petroleum resin, atleast one aliphatic hydrocarbon resin, at least one hydrogenatedaliphatic hydrocarbon resin, at least one aromatic modified aliphatichydrocarbon resin, at least one hydrogenated aromatic modified aliphatichydrocarbon resin, at least one polycyclopentadiene resin, at least onehydrogenated polycyclopentadiene resin, at least one cycloaliphatichydrocarbon resin, at least one hydrogenated cycloaliphatic resin,cycloaliphatic/aromatic hydrocarbon resin, at least one hydrogenatedcycloaliphatic/aromatic hydrocarbon resin, hydrogenated aromatichydrocarbon resin, at least one maleic acid/anhydride modifiedtackifier, terpene modified aromatic and/or aliphatic hydrocarbon resin,at least one hydrogenated terpene modified aromatic and/or aliphatichydrocarbon resin, at least one polyterpene resin, at least onehydrogenated polyterpene resin, at least one aromatic modifiedpolyterpene resin, at least one hydrogenated aromatic modifiedpolyterpene resin, at least one terpene-phenol resin, at least onehydrogenated terpene-phenol resin, at least one gum rosin resin, atleast one hydrogenated gum rosin resin, at least one gum rosin esterresin, at least one wood rosin resin, at least one hydrogenated woodrosin resin, at least one rosin acid resin, at least one hydrogenatedrosin acid resin, or any combination thereof.

In some embodiments, the adhesive formulation comprises 10 wt % to 60 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 20 wt % to 60 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 30 wt % to 60 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 40 wt % to 60 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 50 wt % to 60 wt% of the tackifier based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation comprises 10 wt % to 50 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 10 wt % to 40 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 10 wt % to 30 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 10 wt % to 20 wt% of the tackifier based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation comprises 20 wt % to 50 wt% of the tackifier based on a total weight of the adhesive formulation.In some embodiments, the adhesive formulation comprises 30 wt % to 40 wt% of the tackifier based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation comprises at least onefire retardant.

In some embodiments, the at least one fire retardant comprisescolemanite, aluminum trihydrate, magnesium hydroxide, expandablegraphite, ammonium polyphosphate, triphenyl phosphate, resorcinolbis(diphenylphosphate), bisphenol A diphenyl phosphate, tricresylphosphate, dimethyl methylphosphonate, aluminium diethyl phosphinate,decabromodiphenyl ether, decabromodiphenyl ethane, at least onebrominated polystyrene, at least one brominated carbonate oligomer, atleast one brominated epoxy oligomer, tetrabromophthalic anyhydride,tetrabromobisphenol A, hexabromocyclododecane, antimony trioxide,antimony pentoxide, at least one chlorinated paraffin, huntite,hydromagnesite, red phosphorous, zinc borate, sodium borate, lithiumborate, boric acid, tris(1,3-dichloro-2-propyl)phosphate,tetrakis(2-chlorethyl)dichloroisopentyldiphosphate, or any combinationthereof.

In some embodiments, the at least one fire retardant is present in anamount of 0.1 wt % to 50 wt % based on a total weight of the adhesiveformulation. In some embodiments, the at least one fire retardant ispresent in an amount of 1 wt % to 50 wt % based on a total weight of theadhesive formulation. In some embodiments, the at least one fireretardant is present in an amount of 5 wt % to 50 wt % based on a totalweight of the adhesive formulation. In some embodiments the at least onefire retardant is present in an amount of 10 wt % to 50 wt % based on atotal weight of the adhesive formulation. In some embodiments, the atleast one fire retardant is present in an amount of 20 wt % to 50 wt %based on a total weight of the adhesive formulation. In someembodiments, the at least one fire retardant is present in an amount of30 wt % to 50 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one fire retardant is present in anamount of 40 wt % to 50 wt % based on a total weight of the adhesiveformulation. In some embodiments, the at least one fire retardant ispresent in an amount of 45 wt % to 50 wt % based on a total weight ofthe adhesive formulation.

In some embodiments, the at least one fire retardant is present in anamount of 0.1 wt % to 45 wt % based on a total weight of the adhesiveformulation. In some embodiments the at least one fire retardant ispresent in an amount of 0.1 wt % to 40 wt % based on a total weight ofthe adhesive formulation. In some embodiments, the at least one fireretardant is present in an amount of 0.1 wt % to 30 wt % based on atotal weight of the adhesive formulation. In some embodiments, the atleast one fire retardant is present in an amount of 0.1 wt % to 20 wt %based on a total weight of the adhesive formulation. In someembodiments, the at least one fire retardant is present in an amount of0.1 wt % to 10 wt % based on a total weight of the adhesive formulation.In some embodiments, the at least one fire retardant is present in anamount of 0.1 wt % to 5 wt % based on a total weight of the adhesiveformulation. In some embodiments, the at least one fire retardant ispresent in an amount of 0.1 wt % to 1 wt % based on a total weight ofthe adhesive formulation.

In some embodiments, the at least one fire retardant is present in anamount of 1 wt % to 45 wt % based on a total weight of the adhesiveformulation. In some embodiments, the at least one fire retardant ispresent in an amount of 5 wt % to 40 wt % based on a total weight of theadhesive formulation. In some embodiments, the at least one fireretardant is present in an amount of 10 wt % to 30 wt % based on a totalweight of the adhesive formulation. In some embodiments, the at leastone fire retardant is present in an amount of 20 wt % to 30 wt % basedon a total weight of the adhesive formulation. In some embodiments, theat least one fire retardant is present in an amount of 10 wt % to 20 wt% based on a total weight of the adhesive formulation.

In some embodiments, the adhesive formulation further comprises at leastone filler.

In some embodiments, the at least one filler is calcium carbonate,barium sulfate, calcium sulfate, talc, limestone, perlite, silica, fumedsilica, precipitated silica, quartz, aluminum trihydrate, magnesiumhydroxide, colemanite, titanium dioxide, snow white, fly ash, graphenenanoparticles, carbon black, recycled rubber tires, recycled shingles,recycled thermoplastic resins, basalt, roofing granules, clay, ammoniumpolyphosphate, graphite, or any combination thereof.

In some embodiments, the at least one filler is present in an amountranging from 0.00001% to 70% by weight of the adhesive formulation. Insome embodiments, the at least one filler is present in an amountranging from 0.0001% to 70% by weight of the adhesive formulation. Insome embodiments, the at least one filler is present in an amountranging from 0.001% to 70% by weight of the adhesive formulation. Insome embodiments, the at least one filler is present in an amountranging from 0.01% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.1% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 1% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 10% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 20% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 30% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 40% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 50% to 70% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 60% to 70% by weight of the adhesive formulation.

In some embodiments, the at least one filler is present in an amountranging from 0.00001% to 60% of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 50% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 40% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 30% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 20% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 10% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 1% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 0.1% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 0.01% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 0.001% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.00001% to 0.0001% by weight of the adhesive formulation.

In some embodiments, the at least one filler is present in an amountranging from 0.0001% to 60% by weight of the adhesive formulation. Insome embodiments, the at least one filler is present in an amountranging from 0.001% to 50% by weight of the adhesive formulation. Insome embodiments, the at least one filler is present in an amountranging from 0.01% to 40% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 0.1% to 30% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 1% to 20% by weight of the adhesive formulation. In someembodiments, the at least one filler is present in an amount rangingfrom 5% to 10% by weight of the adhesive formulation.

In some embodiments, the adhesive formulation further comprises at leastone additive. In some embodiments, the at least one additive is at leastone wax, at least one antioxidant, ethylene-bis-stearamide (EBS), or anycombination thereof.

In some embodiments, the at least one additive is present in an amountranging from 0.00001% to 70% by weight of the adhesive formulation. Insome embodiments, the at least one additive is present in an amountranging from 0.0001% to 70% by weight of the adhesive formulation. Insome embodiments, the at least one additive is present in an amountranging from 0.001% to 70% by weight of the adhesive formulation. Insome embodiments, the at least one additive is present in an amountranging from 0.01% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.1% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 1% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 10% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 20% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 30% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 40% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 50% to 70% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 60% to 70% by weight of the adhesive formulation.

In some embodiments, the at least one additive is present in an amountranging from 0.00001% to 60% of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 50% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 40% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 30% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 20% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 10% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 1% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 0.1% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 0.01% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 0.001% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.00001% to 0.0001% by weight of the adhesive formulation.

In some embodiments, the at least one additive is present in an amountranging from 0.0001% to 60% by weight of the adhesive formulation. Insome embodiments, the at least one additive is present in an amountranging from 0.001% to 50% by weight of the adhesive formulation. Insome embodiments, the at least one additive is present in an amountranging from 0.01% to 40% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 0.1% to 30% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 1% to 20% by weight of the adhesive formulation. In someembodiments, the at least one additive is present in an amount rangingfrom 5% to 10% by weight of the adhesive formulation.

In some embodiments, the adhesive achieves at least a passing grade whentested according to ASTM D1970 at a predetermined test temperature

In some embodiments, the passing grade under ASTM D1970 is 1 lb/ft atthe predetermined test temperature of 40° F. In some embodiments, thepassing grade under ASTM D1970 is 2 lb/ft at the predetermined testtemperature of 40° F. In some embodiments, the passing grade under ASTMD1970 is 3 lb/ft at the predetermined test temperature of 40° F. In someembodiments, the passing grade under ASTM D1970 is 4 lb/ft at thepredetermined test temperature of 40° F. In some embodiments, thepassing grade under ASTM D1970 is 5 lb/ft at the predetermined testtemperature of 40° F.

In some embodiments, the passing grade under ASTM D1970 is 10 lb/ft atthe predetermined test temperature of 75° F. In some embodiments, thepassing grade under ASTM D1970 is 11 lb/ft at the predetermined testtemperature of 75° F. In some embodiments, the passing grade under ASTMD1970 is 12 lb/ft at the predetermined test temperature of 75° F. Insome embodiments, the passing grade under ASTM D1970 is 13 lb/ft at thepredetermined test temperature of 75° F. In some embodiments, thepassing grade under ASTM D1970 is 14 lb/ft at the predetermined testtemperature of 75° F. In some embodiments, the passing grade under ASTMD1970 is 15 lb/ft at the predetermined test temperature of 75° F.

In some embodiments, the adhesive formulation achieves a mechanicaluplift of at least 20 lb/ft when tested according to ASTM D6381 afterbeing conditioned at 140° F. for 16 hours. In some embodiments, theadhesive formulation achieves a mechanical uplift of at least 30 lb/ftwhen tested according to ASTM D6381 after being conditioned at 140° F.for 16 hours. In some embodiments, the adhesive formulation achieves amechanical uplift of at least 40 lb/ft when tested according to ASTMD6381 after being conditioned at 140° F. for 16 hours. In someembodiments, the adhesive formulation achieves a mechanical uplift of atleast 50 lb/ft when tested according to ASTM D6381 after beingconditioned at 140° F. for 16 hours. In some embodiments, the adhesiveformulation achieves a mechanical uplift of at least 60 lb/ft whentested according to ASTM D63 81 after being conditioned at 140° F. for16 hours. In some embodiments, the adhesive formulation achieves amechanical uplift of at least 60 lb/ft when tested according to ASTMD6381 after being conditioned at 140° F. for 16 hours. In someembodiments, the adhesive formulation achieves a mechanical uplift of atleast 70 lb/ft when tested according to ASTM D6381 after beingconditioned at 140° F. for 16 hours. In some embodiments, the adhesiveformulation achieves a mechanical uplift of at least 80 lb/ft whentested according to ASTM D6381 after being conditioned at 140° F. for 16hours. In some embodiments, the adhesive formulation achieves amechanical uplift of at least 90 lb/ft when tested according to ASTMD6381 after being conditioned at 140° F. for 16 hours.

In some embodiments, the adhesive formulation achieves a mechanicaluplift of 20 lb/ft to 100 lb/ft when tested according to ASTM D6381after being conditioned at 140° F. for 16 hours. In some embodiments,the adhesive formulation achieves a mechanical uplift of 30 lb/ft to 100lb/ft when tested according to ASTM D6381 after being conditioned at140° F. for 16 hours. In some embodiments, the adhesive formulationachieves a mechanical uplift of 40 lb/ft to 100 lb/ft when testedaccording to ASTM D6381 after being conditioned at 140° F. for 16 hours.In some embodiments, the adhesive formulation achieves a mechanicaluplift of 50 lb/ft to 100 lb/ft when tested according to ASTM D6381after being conditioned at 140° F. for 16 hours. In some embodiments,the adhesive formulation achieves a mechanical uplift of 60 lb/ft to 100lb/ft when tested according to ASTM D6381 after being conditioned at140° F. for 16 hours. In some embodiments, the adhesive formulationachieves a mechanical uplift of 70 lb/ft to 100 lb/ft when testedaccording to ASTM D6381 after being conditioned at 140° F. for 16 hours.In some embodiments, the adhesive formulation achieves a mechanicaluplift of 80 lb/ft to 100 lb/ft when tested according to ASTM D6381after being conditioned at 140° F. for 16 hours. In some embodiments,the adhesive formulation achieves a mechanical uplift of 90 lb/ft to 100lb/ft when tested according to ASTM D6381 after being conditioned at140° F. for 16 hours.

In some embodiments, the adhesive formulation achieves a mechanicaluplift of 20 lb/ft to 90 lb/ft when tested according to ASTM D6381 afterbeing conditioned at 140° F. for 16 hours. In some embodiments, theadhesive formulation achieves a mechanical uplift of 20 lb/ft to 80lb/ft when tested according to ASTM D6381 after being conditioned at140° F. for 16 hours. In some embodiments, the adhesive formulationachieves a mechanical uplift of 20 lb/ft to 70 lb/ft when testedaccording to ASTM D6381 after being conditioned at 140° F. for 16 hours.In some embodiments, the adhesive formulation achieves a mechanicaluplift of 20 lb/ft to 60 lb/ft when tested according to ASTM D6381 afterbeing conditioned at 140° F. for 16 hours. In some embodiments, theadhesive formulation achieves a mechanical uplift of 20 lb/ft to 50lb/ft when tested according to ASTM D6381 after being conditioned at140° F. for 16 hours. In some embodiments, the adhesive formulationachieves a mechanical uplift of 20 lb/ft to 40 lb/ft when testedaccording to ASTM D6381 after being conditioned at 140° F. for 16 hours.In some embodiments, the adhesive formulation achieves a mechanicaluplift of 20 lb/ft to 30 lb/ft when tested according to ASTM D6381 afterbeing conditioned at 140° F. for 16 hours.

In some embodiments, the adhesive formulation achieves a mechanicaluplift of 30 lb/ft to 90 lb/ft when tested according to ASTM D6381 afterbeing conditioned at 140° F. for 16 hours. In some embodiments, theadhesive formulation achieves a mechanical uplift of 40 lb/ft to 80lb/ft when tested according to ASTM D6381 after being conditioned at140° F. for 16 hours. In some embodiments, the adhesive formulationachieves a mechanical uplift of 50 lb/ft to 70 lb/ft when testedaccording to ASTM D6381 after being conditioned at 140° F. for 16 hours.

In some embodiments, the adhesive formulation may exhibit a specifiedactivation temperature. As used herein, “activation temperature” is theminimum temperature at which the value of tan δ of a given formulationexceeds 1; where tan δ0 is a ratio of G″ to G′, where G″ is the lossmodulus of a given formulation, and where G′ is the storage modulus ofthe same formulation. In some embodiments, a tan δ0 value of greaterthan 1 indicates that an adhesive formulation is present at a sufficienttemperature to form a bond with a material.

In some embodiments, the adhesive formulation may exhibit an activationtemperature of 15° F. to 60° F. In some embodiments, the adhesiveformulation may exhibit an activation temperature of 30° F. to 60° F. Insome embodiments, the adhesive formulation may exhibit an activationtemperature of 45° F. to 60° F.

In some embodiments, the adhesive formulation may exhibit an activationtemperature of 15° F. to 45° F. In some embodiments, the adhesiveformulation may exhibit an activation temperature of 15° F. to 30° F.

In some embodiments, the adhesive formulation may exhibit an activationtemperature of 30° F. to 45° F.

In some embodiments, the adhesive formulation may exhibit a specifiedDahlquist Criterion Temperature. As used herein, the “DahlquistCriterion Temperature” is the minimum temperature at which a givenformulation achieves a G′ (i.e., storage modulus) of greater than 300kPa. The Dahlquist criterion temperature is measured herein pursuant tothe procedures discussed in Ir. Roelof Luth, “Defining ViscoelasticAdhesive Coordinates that Matter,”https://www.pstc.org/files/public/Luth_Roelof.pdf, which is incorporatedby reference herein in its entirety for all purposes.

In some embodiments, the adhesive formulation exhibits a DahlquistCriterion Temperature of 35° F. to 65° F. In some embodiments, theadhesive formulation exhibits a Dahlquist Criterion Temperature of 45°F. to 65° F. In some embodiments, the adhesive formulation exhibits aDahlquist Criterion Temperature of 55° F. to 65° F.

In some embodiments, the adhesive formulation exhibits a DahlquistCriterion Temperature of 35° F. to 55° F. In some embodiments, theadhesive formulation exhibits a Dahlquist Criterion Temperature of 35°F. to 45° F.

In some embodiments, the adhesive formulation exhibits a DahlquistCriterion Temperature of 45° F. to 55° F.

In some embodiments, the adhesive formulation may exhibit a specifiedpeel strength. As used herein, “peel strength” is measured is measuredaccording to the procedure discussed in F. A. Mazzeo, “Characterizationof Pressure Sensitive Adhesives by Rheology,” TA Instruments ReportRH082 (2002), pages 1-8, which is referenced by S. Sun et al., “A reviewof mechanical properties of pressure sensitive adhesives,” InternationalJournal of Adhesion and Adhesives, 41 (2013), pages 98-106, both ofwhich are incorporated by reference herein in their respectiveentireties for all purposes.

In some embodiments, the adhesive formulation has a peel strength of 7.5MPa to 50 MPa measured at 25° C. In some embodiments, the adhesiveformulation has a peel strength of 15 MPa to 50 MPa measured at 25° C.In some embodiments, the adhesive formulation has a peel strength of 25MPa to 50 MPa measured at 25° C. In some embodiments, the adhesiveformulation has a peel strength of 45 MIPa to 50 MPa measured at 25° C.

In some embodiments, the adhesive formulation has a peel strength of 15MPa to 50 MPa measured at 25° C. In some embodiments, the adhesiveformulation has a peel strength of 25 MPa to 50 MPa measured at 25° C.In some embodiments, the adhesive formulation has a peel strength of 45MPa to 50 MPa measured at 25° C.

In some embodiments, the adhesive formulation has a peel strength of 15MPa to 45 MPa measured at 25° C. In some embodiments, the adhesiveformulation has a peel strength of 25 MPa to 45 MPa measured at 25° C.

Some embodiments of the present disclosure relate to a method of makingan adhesive that is free or substantially free of asphalt.

In some embodiments, the method comprises combining at least one processoil and at least one polymer. In some embodiments, the method comprisescombining limestone powder with at least one process oil and at leastone polymer. In some embodiments, the method comprises combining atleast one tackifier with at least one process oil and at least onepolymer. In some embodiments, the method comprises combining at leastone tackifier with limestone powder, at least one process oil and atleast one polymer. In some embodiments the components of an adhesiveformulation are combined sequentially, all at once, or any combinationthereof. In some embodiments, the method comprises forming the adhesiveformulation into a flowable adhesive formulation.

In some embodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 1,000 cP to 10,000 cP tested at 374°F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 60 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 2,000 cPto 10,000 cP tested at 374° F., using a Brookfield viscometer withspindle number LV-4, and a viscometer speed of 60 RPM. In someembodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 5,000 cP to 10,000 cP tested at 374°F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 60 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 9,000 cPto 10,000 cP tested at 374° F., using a Brookfield viscometer withspindle number LV-4, and a viscometer speed of 60 RPM.

In some embodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 1,000 cP to 9,000 cP tested at 374°F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 60 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 1,000 cPto 5,000 cP tested at 374° F., using a Brookfield viscometer withspindle number LV-4, and a viscometer speed of 60 RPM. In someembodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 1,000 cP to 2,000 cP tested at 374°F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 60 RPM.

In some embodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 2,000 cP to 9,000 cP tested at 374°F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 60 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 5,000 cPtested at 374° F., using a Brookfield viscometer with spindle numberLV-4, and a viscometer speed of 60 RPM.

In some embodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 10,000 cP to 30,000 cP tested at374° F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 30 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 15,000 cPto 30,000 cP tested at 374° F., using a Brookfield viscometer withspindle number LV-4, and a viscometer speed of 30 RPM. In someembodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 20,000 cP to 30,000 cP tested at374° F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 30 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 25,000 cPto 30,000 cP tested at 374° F., using a Brookfield viscometer withspindle number LV-4, and a viscometer speed of 30 RPM.

In some embodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 10,000 cP to 25,000 cP tested at374° F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 30 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 10,000 cPto 20,000 cP tested at 374° F., using a Brookfield viscometer withspindle number LV-4, and a viscometer speed of 30 RPM. In someembodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 10,000 cP to 15,000 cP tested at374° F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 30 RPM.

In some embodiments, the flowable adhesive formulation is an adhesiveformulation that has a viscosity of 15,000 cP to 25,000 cP tested at374° F., using a Brookfield viscometer with spindle number LV-4, and aviscometer speed of 30 RPM. In some embodiments, the flowable adhesiveformulation is an adhesive formulation that has a viscosity of 20,000 cPtested at 374° F., using a Brookfield viscometer with spindle numberLV-4, and a viscometer speed of 30 RPM.

In some embodiments, the forming of the flowable adhesive formulationcomprises heating the adhesive formulation to a temperature of 300° F.to 400° F. In some embodiments, the forming of the flowable adhesiveformulation comprises heating the adhesive formulation to a temperatureof 325° F. to 400° F. In some embodiments, the forming of the flowableadhesive formulation comprises heating the adhesive formulation to atemperature of 350° F. to 400° F. In some embodiments, the forming ofthe flowable adhesive formulation comprises heating the adhesiveformulation to a temperature of 375° F. to 400° F.

In some embodiments, the forming of the flowable adhesive formulationcomprises heating the adhesive formulation to a temperature of 300° F.to 375° F. In some embodiments, the forming of the flowable adhesiveformulation comprises heating the adhesive formulation to a temperatureof 300° F. to 350° F. In some embodiments, the forming of the flowableadhesive formulation comprises heating the adhesive formulation to atemperature of 300° F. to 325° F.

In some embodiments, the forming of the flowable adhesive formulationcomprises heating the adhesive formulation to a temperature of 325° F.to 375° F. In some embodiments, the forming of the flowable adhesiveformulation comprises heating the adhesive formulation to a temperatureof 350° F.

Some embodiments of the present disclosure relate to a method of usingan adhesive formulation that is free or substantially free of asphalt.

In some embodiments, the method comprises applying the adhesiveformulation to at least one surface of a substrate. In some embodiments,the substrate is a roof substrate. In some embodiments, the substrate orroof substrate is a plywood substrate, a glass substrate, a fiberglasssubstrate, (e.g., a fiberglass mat), a cellulosic substrate, a shingle(e.g., a roofing shingle), an underlayment, a roofing membrane (e.g., athermoplastic polyolefin (TPO) or polyvinyl chloride (PVC) membrane), aroof deck, a photovoltaic (PV) panel, a modified bitumen (MODBIT)substrate, an ethylene tetrafluoroethylene (ETFE) substrate, a rollgood, or any combination thereof.

In some embodiments, the method comprises using the adhesive formulationto seal a leak. In some embodiments, the leak is present on a surface ofa substrate (such as but not limited to a roof substrate), betweenmultiple surfaces of a substrate (such as but not limited to a roofsubstrate), between multiple substrates or any combination thereof. Insome embodiments, the leak is present between two surfaces of asubstrate. In some embodiments, the leak is present between threesurfaces of a substrate. In some embodiments, the leak is presentbetween four surfaces of a substrate. In some embodiments, the leak ispresent between two substrates. In some embodiments, the leak is presentbetween three substrates. In some embodiments, the leak is presentbetween four substrates.

In some embodiments, the method further comprises forming the adhesiveformulation into at least one adhesive sheet, forming the adhesive intoat least one adhesive strip, or any combination thereof. In someembodiments, the forming of the adhesive formulation into at least oneadhesive sheet, the forming the adhesive into at least one adhesivestrip, or any combination thereof comprises casting the adhesiveformulation into the at least one adhesive sheet, casting the adhesiveformulation into the at least one adhesive strip, or any combinationthereof. In some embodiments, the casting is performed with a rollermill.

For instance, as shown in FIG. 1, an exemplary adhesive formulation maytake the form of a strip 101. In some embodiments, the strip 101 may bebonded to substrate 102. In some embodiments, the strip 101 may bondsubstrate 102 to second substrate 103.

Some embodiments of the present disclosure relate to a system comprisinga substrate and an adhesive formulation that is present on at least onesurface of the substrate, where the adhesive formulation is free orsubstantially free of asphalt. In some embodiments, the substrate is anysubstrate described herein. In some embodiments, the system comprisesmultiple substrates, such as but not limited to, any combination ofsubstrates described herein.

In some embodiments, the first substrate and the second substrate arethe same. In some embodiments, the first substrate and the secondsubstrate are different. In some embodiments, the first roofingsubstrate, the second roofing substrate, or any combination thereof is aroofing shingle.

Among those benefits and improvements that have been disclosed, otherobjects and advantages of this disclosure will become apparent from thefollowing description taken in conjunction with the accompanyingfigures. Detailed embodiments of the present disclosure are disclosedherein; however, it is to be understood that the disclosed embodimentsare merely illustrative of the disclosure that may be embodied invarious forms. In addition, each of the examples given regarding thevarious embodiments of the disclosure which are intended to beillustrative, and not restrictive.

Throughout the specification and claims, the following terms take themeanings explicitly associated herein, unless the context clearlydictates otherwise. The phrases “in one embodiment,” “in an embodiment,”and “in some embodiments” as used herein do not necessarily refer to thesame embodiment(s), though it may. Furthermore, the phrases “in anotherembodiment” and “in some other embodiments” as used herein do notnecessarily refer to a different embodiment, although it may. Allembodiments of the disclosure are intended to be combinable withoutdeparting from the scope or spirit of the disclosure.

As used herein, the term “based on” is not exclusive and allows forbeing based on additional factors not described, unless the contextclearly dictates otherwise. In addition, throughout the specification,the meaning of “a,” “an,” and “the” include plural references. Themeaning of “in” includes “in” and “on.”

As used herein, terms such as “comprising” “including,” and “having” donot limit the scope of a specific claim to the materials or stepsrecited by the claim.

As used herein, the phrase “consisting essentially of” limits the scopeof a specific claim to the specified materials or steps and those thatdo not materially affect the basic and novel characteristic orcharacteristics of the specific claim. In one non-limiting example, aspecific claim reciting “consisting essentially of” allows for theaddition of a non-recited claim element, so long as the non-recitedclaim element is “free or substantially free of asphalt,” as definedherein. In another non-limiting example, a specific claim reciting“consisting essentially of” allows for the addition of a non-recitedclaim element, so long as the non-recited claim element achieves amechanical uplift of at least 20 lb/ft when tested according to ASTMD6381 after being conditioned at 140° F. for 16 hours, wherein theadhesive formulation achieves at least a passing grade of 2 lb/ft whentested according to ASTM D1970 at a specific test temperature of 40° F.,wherein the adhesive formulation achieves at least a passing grade of 12lb/ft when tested according to ASTM D1970 at a specific test temperatureof 75° F., or any combination thereof. As used herein and when used inthe context of a claim reciting the term “consisting essentially of,”the term “optionally” denotes a non-limiting example of a claim elementthat does not materially affect the basic and novel characteristic orcharacteristics of the specific claim.

As used herein, terms such as “consisting of” and “composed of” limitthe scope of a specific claim to the materials and steps recited by theclaim.

EXAMPLE 1

At least one process oil was blended with at least one polymer in a highshear mixer until smooth and then transferred to a paddle mixer, wherelimestone powder was added. In some samples, additional components, suchas but not limited to filler(s) and additive(s) were also added. Theresulting adhesive formulations, which were free of asphalt, were castin between 2 mil rollers with release paper on both sides. The adhesiveformulations were poured on a 1.88 lbs/100 sq. ft nonwoven glass matsubstrate for a topcoat of the adhesive formulation at 10 mils and thenpoured between the 2 mil rollers on the back side for another 10 mils tomake the bottom coat, thereby forming an adhesive substrate. For anadhesive substrate having a single coat construction, the same compoundwas used to pour the top and back of the adhesive substrate. For a dualcoat construction, the topcoat was a different adhesive formulation thanthe bottom coat. The finished adhesive substrates were then cooled, cutand tested for ASTM D1970 plywood peel adhesion at three differentconditions (40° F., 73° F. and 140° F.). A portion of each adhesivesubstrate was also put into a 120° F. convection oven to condition for 2weeks and then tested for plywood adhesion to obtain aged peel valuesunder ASTM D1970. Results are shown in Tables 1A and 1B below.

TABLE 1A Formulation 3 (dual Form- Form- coat applied to Ply- ulationulation wood in ASTM test) Component Unit 1 2 Coat 1 Coat 2 Asphalt Fluxwt. % 0 0 0 0 (CAS# 8052- 42-4) Bright Stock wt. % 55 53 40 50 ExtractIsotactic wt. % 0 0 0 0 Polypropylene SBS wt. % 10 12 5 10 Copolymer(Radial Block) Limestone wt. % 35 35 55 40 Viscosity @ cP 2200 6400 15003800 374 F. (LVT) ASTM D1970 lb./ft. 104.8 ± 7.6 55.8 ± 6.9 54 ± 19 180°Plywood Peel Tested @ 40 F. ASTM D1970 lb./ft.  36.8 ± 8.9  6.7 ± 3.2  6 ± 1.2 180° Plywood Peel Tested @ 73 F. ASTM D1970 lb./ft.  6.9 ± 2.11.5 ± .9 3.5 ± 1.9 180° Plywood Peel Tested @ 140 F. 

TABLE 1B Form- Form- Form- Form- Component Unit ulation 4 ulation 5ulation 6 ulation 7 Asphalt Flux wt. % 0 0 0 0 (CAS# 8052- 42-4) BrightStock wt. % 50 53 45 40 Extract Isotactic wt. % 0 2 0 0 PolypropyleneSBS wt. % 10 10 10 10 Copolymer (Radial Block) Limestone wt. % 40 35 4550 Viscosity @ cP 4300 5400 8300 6900 374 F. (LVT) ASTM D1970 lb./ft.87.8 ± 82.4 ± 14.2 69.2 ± 7.4 64.1 ± 9.3  180° Plywood 13.2 Peel Tested@ 40 F. ASTM D1970 lb./ft. 30.1 ± 3.4 37.8 ± 3.4  23.5 ± 4.5 19.8 ± 2.5 180° Plywood Peel Tested @ 73 F. ASTM D1970 lb./ft. 10.1 ± 2.3 4.4 ± 1.710.5 ± 1.9 4.3 ± 1.4 180° Plywood Peel Tested @ 140 F. 

COMPARATIVE EXAMPLE 1

The same steps of Example 1 were performed except that the adhesiveformulations were comparative formulations that included asphalt.Results are shown in Table 1C below.

TABLE 1C Comparative Comparative Comparative Formulation Form-Formulation Component Unit 1 ulation 2 3 Asphalt Flux wt. % 77 57 43(CAS# 8052-42-4) Bright Stock Extract wt. % 0 0 0 IsotacticPolypropylene wt. % 0 0 0 SBS Copolymer wt. % 8 8 7 (Radial Block)Limestone wt. % 15 35 50 Viscosity @ 374 F. cP 2100 14000 260000 (LVT)ASTM D1970 180° lb./ft. 80 ± 6  27.6 ± 12.9 4 Plywood Peel Tested @ 40F. ASTM D1970 180° lb./ft. 52 ± 14 46.4 ± 15.4 0 Plywood Peel Tested @73 F. ASTM D1970 180° lb./ft. 2.5 ± .5  1.6 ± .7  0 Plywood Peel Tested@ 140 F.

EXAMPLE 2

An additional exemplary formulation “Formulation 8,” that was free orsubstantially free of asphalt, included the following components—44%Sylfat DP-8 (tall oil pitch, low sterols); 44% Sylvatac RE-98(pentaerythritol rosin esters); 10% D-1184 KT (radial SBS polymer); and2% G-1650 (linear SEBS polymer).

The formulation was prepared using the following procedure.

A high shear (Silverson) mixing set-up was assembled, along with a quartcan-sized heating mantle and temperature controller. To the quart can,310.70 g of Sylfat DP-8 (Kraton® Chemical) was added. The can wasinserted into the heating mantle, and the mixing head was immersed intothe tall oil pitch. A thermocouple attached to the temperaturecontroller was inserted into the tall oil pitch. The mixer was set to aspeed of 250-500 rpm and the temperature controller was set to a targettemperature of 180° C. Once the temperature reached 180° C., 310.74 g ofSylvatac RE-98 (Kraton® Chemical) was slowly added into the DP-8 withcontinuous mixing. After the RE-98 was incorporated into the blend, themixing speed was increased to 2500-3000 rpm and 70.64 g of D-1184(Kraton® Polymer) was slowly added into the liquid. Afterwards, 14.12 gof G-1650 (Kraton® Polymer) was slowly added to the mixture. Mixing at2500 to 3000 rpm was continued for 1 hour. The can was then removed fromthe high shear mixing set-up. The can was transferred to a heatingmantle attached to a temperature controller and a low shear mixer set-upwas put together above it. A paddle blade was immersed into the liquidand a thermocouple was inserted into the liquid. Mixing was maintainedbetween 500-600 rpm and the temperature was kept at 180° C. for 3 hours,for a total of 4 hours of combined mixing at one or more mixing speedschosen from 250-600 rpm, 2500-3000 rpm, or any combination thereof. Thesample can was removed from the mixing and heating set-up and sampleswere prepared for testing.

An additional exemplary formulation “Formulation 9,” that was free orsubstantially free of asphalt, contained the following components-44%Sylfat DP-1 (tall oil pitch), 44% Dertoline P110 (maleatedpentaerythritol rosin esters), 10% D-1184 (radial SBS polymer), 2%G-1650 (linear SEBS polymer).

The formulation was prepared using the following procedure.

A high shear (Silverson) mixing set-up was assembled, along with a quartcan-sized heating mantle and temperature controller. To the quart can,316.12 g of Sylfat DP-1 (Kraton Chemical) was added. The can wasinserted into the heating mantle, and the mixing head was immersed intothe tall oil pitch. A thermocouple attached to the temperaturecontroller was inserted into the tall oil pitch. The mixer was set to aspeed of 250-500 rpm and the temperature controller was set to a targettemperature of 180° C. Once the temperature reached 180° C., 316.13 g ofDertoline P110 (DRT) was slowly added into the DP-1 with continuousmixing. After the P110 was incorporated into the blend, the mixing speedwas increased to 2500-3000 rpm and 71.84 g of D-1184 (Kraton Polymer)was slowly added into the liquid. Afterwards, 14.39 g of G-1650 (KratonPolymer) was slowly added to the mixture. High shear mixing wascontinued for 1 hour. The can was then removed from the high shearmixing set-up. The can was transferred to a heating mantle attached to atemperature controller and a low shear mixer set-up was put togetherabove it. A paddle blade was immersed into the liquid and a thermocouplewas inserted into the liquid. Mixing was maintained between 500-600 rpmand the temperature was kept at 180° C. for 3 hours, for a total of 4hours of combined mixing at one or more mixing speeds chosen from250-600 rpm, 2500-3000 rpm, or any combination thereof. The sample canwas removed from the mixing and heating set-up and samples were preparedfor testing.

Properties of Formulations 8 and 9 were tested and shown in Table 2Abelow. Table 2A also shows the corresponding properties of twocomparative formulations—Comparative Formulation 4, which is anasphaltic adhesive commercially available from US Polyco™ as USP 3120;and Comparative Formulation 5, which is commercially available fromParker Hannifin as LORD HM 17-1.

TABLE 2A Activation Dahlquist Peel Temperature, Criterion Strength atFormulation (° F.) Temperature, (° F.) 25° C. (MPa) Comparative 4 63.568 7.3 Comparative 5 14 32 1.4 8 45 50 9.9 9 45 63.5 7.9

Specifically, Table 2A, above, shows some data related to adhesivematerial performance, comparing the exemplary Formulations 8 and 9 withcomparative Formulations 4 and 5.

Samples adhered using Formulation 8 and Comparative Formulations 6-8were tested for shear strength and peel strength at 90° . The resultsare shown in Table 3. The adhesives were applied between an ethylenetetrafluoroethylene (ETFE) substrate and a thermoplastic polyolefin(TPO) substrate to form the samples. The ETFE substrate was adhered to aglass substrate to provide rigidity to the samples. The adhesives wereapplied in a region of approximately 1 square inch between the ETFEsubstrate and the TPO substrate. The shear strength test was performedusing a test system commercially available from Instron®. The sampleswere preloaded at a rate of 20 mm/min until reaching 1 N of force, thentested at a rate of 50 mm/min until failure. The shear strength wastested at TO at which the samples had not been artificially aged. Theshear strength was also tested after 500 hours of aging at 135° C. Afterthe 500 hours, the samples were returned to room temperature beforetesting the shear strength of the aged samples. The peel strength at 90°was obtained by lifting the TPO at 90° from the ETFE substrate. Anexample of the samples is shown in FIG. 2. As shown in a side view, aglass substrate 202 is fixed to an ETFE substrate 204. Adhesive 206 isapplied between the ETFE substrate 204 and a TPO substrate 208.

TABLE 3 Shear Peel Strength at T0 Shear Strength at Strength at 90° (N)T = 500 hours (N) (N/cm) Formulation 8 275 440 20 Comparative 220 280 2Formulation 6 Comparative 240 175 1 Formulation 7 Comparative 180 375 1Formulation 8

Comparative Formulations 6-8 each included greater than 90% asphalt. Assuch, each of the comparative formulations can be generally referred toas “asphalt-based adhesives.” As shown in Table 3, samples utilizingFormulation 8 exhibited higher shear strengths (both before and afteraging) and higher peel strengths at 90° than the samples using theComparative Formulations 6-8.

All prior patents, publications, and test methods referenced herein areincorporated by reference in their entireties. Variations, modificationsand alterations to embodiments of the present disclosure described abovewill make themselves apparent to those skilled in the art. All suchvariations, modifications, alterations and the like are intended to fallwithin the spirit and scope of the present disclosure, limited solely bythe appended claims.

While several embodiments of the present disclosure have been described,it is understood that these embodiments are illustrative only, and notrestrictive, and that many modifications may become apparent to those ofordinary skill in the art. For example, all dimensions discussed hereinare provided as examples only, and are intended to be illustrative andnot restrictive.

Any feature or element that is positively identified in this descriptionmay also be specifically excluded as a feature or element of anembodiment of the present as defined in the claims.

The disclosure described herein may be practiced in the absence of anyelement or elements, limitation or limitations, which is notspecifically disclosed herein. Thus, for example, in each instanceherein, any of the terms “comprising,” “consisting essentially of” and“consisting of” may be replaced with either of the other two terms,without altering their respective meanings as defined herein. The termsand expressions which have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of thedisclosure.

What is claimed is:
 1. A roofing system, comprising: a substrate; and anadhesive formulation, wherein the adhesive formulation is present on atleast one surface of the substrate, and wherein the adhesive formulationcomprises: 10 wt % to 70 wt % of a filler, at least one tackifier, orany combination thereof, based on a total weight of the adhesiveformulation; 20 wt % to 70 wt % of at least one process oil based on thetotal weight of the adhesive formulation; 0.1 wt % to 50 wt % of atleast one fire retardant, based on the total weight of the adhesiveformulation; and 0.5 wt % to 30 wt % of at least one polymer, based onthe total weight of the adhesive formulation; wherein the adhesiveformulation is free of asphalt or substantially free of asphalt.
 2. Theroofing system of claim 1, wherein the substrate is a plywood substrate,a glass substrate, a fiberglass substrate, a cellulosic substrate, ashingle, an underlayment, a roofing membrane, a roof deck, aphotovoltaic (PV) panel, a modified bitumen (MODBIT) substrate, a rolledgood, or any combination thereof.
 3. The roofing system of claim 1,wherein the at least one process oil is chosen from at least oneparaffinic oil, at least one petroleum extract, at least one vegetableoil, at least one naphthenic oil, at least one aromatic oil, at leastone re-refined engine oil bottom (REOB), at least one engine oil residue(EOR), at least one re-refined heavy vacuum distillation bottom (RHVDB),at least one re-refined heavy vacuum distillation oil (RHVDO), at leastone re-refined vacuum tower bottom (RVTB), at least one vacuum towerbottom (VTB), at least one tall oil, or any combination thereof.
 4. Theroofing system of claim 1, wherein the at least one polymer is astyrene-butadiene-styrene (SBS) copolymer.
 5. The roofing system ofclaim 4, wherein the at least one polymer is present in an amount of 5wt % to 15 wt %, based on the total weight of the adhesive formulation,wherein the at least one process oil is present in an amount of 40 wt.%to 50 wt.% based on the total weight of the adhesive formulation.
 6. Theroofing system of claim 4, wherein the adhesive formulation furthercomprises at least one second polymer chosen from: at least onepolyolefin, oxidized polyethylene (OPE), polyethylene-polypropyleneelastomer, ground tire rubber (GTR), isotactic polypropylene (IPP),atactic polypropylene (APP), or any combination thereof.
 7. The roofingsystem of claim 6, wherein the at least one second polymer is present inan amount of 0.1 wt % to 20 wt %, based on the total weight of theadhesive formulation.
 8. The roofing system of claim 1, wherein thefiller is limestone powder, calcium carbonate, barium sulfate, calciumsulfate, talc, perlite, silica, fumed silica, precipitated silica,quartz, aluminum trihydrate, magnesium hydroxide, colemanite, titaniumdioxide, snow white, fly ash, graphene nanoparticles, carbon black,recycled rubber tires, recycled shingles, recycled thermoplastic resins,basalt, roofing granules, clay, ammonium polyphosphate, graphite, or anycombination thereof.
 9. The roofing system of claim 1, wherein thefiller is limestone powder.
 10. The roofing system of claim 1, whereinthe adhesive formulation further comprises at least one additive in anamount ranging from 0.00001% to 70% by weight of the adhesiveformulation.
 11. The roofing system of claim 10, wherein the at leastone additive is at least one wax, at least one antioxidant,ethylene-bis-stearamide (EBS), or any combination thereof.
 12. Theroofing system of claim 1, wherein the at least one fire retardant isammonium polyphosphate.
 13. A method, comprising: combining a fillerwith at least one process oil and at least one polymer, so as to form anadhesive formulation, wherein the adhesive formulation comprises: 10 wt% to 70 wt % of the filler, based on a total weight of the adhesiveformulation; 20 wt % to 70 wt % of the at least one process oil, basedon the total weight of the adhesive formulation; and 0.5 wt % to 30 wt %of the at least one polymer, based on the total weight of the adhesiveformulation; wherein the adhesive formulation is free of asphalt orsubstantially free of asphalt.
 14. The method of claim 13, wherein theat least one process oil is chosen from at least one paraffinic oil, atleast one petroleum extract, at least one vegetable oil, at least onenaphthenic oil, at least one aromatic oil, at least one re-refinedengine oil bottom (REOB), at least one engine oil residue (EOR), atleast one re-refined heavy vacuum distillation bottom (RHVDB), at leastone re-refined heavy vacuum distillation oil (RHVDO), at least onere-refined vacuum tower bottom (RVTB), at least one vacuum tower bottom(VTB), at least one tall oil, or any combination thereof.
 15. The methodof claim 13, wherein the at least one polymer is astyrene-butadiene-styrene (SBS) copolymer.
 16. The method of claim 15,wherein the at least one polymer is present in an amount of 0.5 wt % to30 wt %, based on the total weight of the adhesive formulation.
 17. Themethod of claim 16, wherein the adhesive formulation further comprisesat least one second polymer present in an amount of 0.1 wt % to 20 wt %,based on the total weight of the adhesive formulation, wherein the atleast one second polymer is chosen from: at least one polyolefin,oxidized polyethylene (OPE), polyethylene-polypropylene elastomer,ground tire rubber (GTR), isotactic polypropylene (IPP), atacticpolypropylene (APP), or any combination thereof.
 18. The method of claim13, further comprising 0.1 wt % to 50 wt % of at least one fireretardant, based on the total weight of the adhesive formulation.
 19. Amethod, comprising: obtaining a roofing substrate; and obtaining anadhesive formulation, wherein the adhesive formulation comprises: 10 wt% to 70 wt % of a filler, at least one tackifier, or any combinationthereof, based on a total weight of the adhesive formulation; 20 wt % to70 wt % of at least one process oil, based on the total weight of theadhesive formulation; 0.1 wt % to 50 wt % of at least one fireretardant, based on the total weight of the adhesive formulation; 0.5 wt% to 30 wt % of at least one polymer, based on the total weight of theadhesive formulation; wherein the adhesive formulation is free ofasphalt or substantially free of asphalt; and applying the adhesiveformulation to at least one surface of the roofing substrate.
 20. Themethod of claim 19, wherein the roofing substrate is a plywoodsubstrate, a glass substrate, a fiberglass substrate, a cellulosicsubstrate, a shingle, an underlayment, a roofing membrane, a roof deck,a photovoltaic (PV) panel, a modified bitumen (MODBIT) substrate, arolled good, or any combination thereof.